Dyeing with vat dyes



Patented Jan. 19, 1937 UNITED STATES PATENT oFFic DYEING WITH VAT DYES A Jean G. Kern, Hamburg, N. Y., assignor to Na-.

tional Aniline & Chemi a corporation of New York Application April 8, 1935, Serial York, N. Y.,

W No Drawing.

cal Company, Inc., New

No. 15,263. In Great Britain, May 25, 1934 Milaims.

This invention relates to the art of dyeing with vat dyes. It relates especially to a new class of assistants for the dyeing of textile fibers, and especially those of the vegetable type, such I 5 as cotton, regenerated cellulose and the like, with vat dyes by means of a dye bath or dye liq-.

uor containing a vat dye in the reduced form, whereby dyeings of excellent fastness, penetration, depth and brilliance may be obtained.

As is well known, vat dyes are solid substances which are insoluble in water. In the dyeing of textile fibers with vat dyes, the insoluble vat dyes are converted to a reduced form, in which form they are taken up by the fiber, and then the fiber is subjected to an oxidizing or fixing treatment whereby the dyestuif is again rendered insoluble. In general, the dyeing processv involves treatment of the fiber to be dyed with the dye bath or dye liquor, containing the re 0 duced compound (leuco-compound) of the vat dye. A number of procedures are employed in carrying out the process, as for example, working piece goods (cotton, regenerated cellulose, etc.) and raw cotton stock (unspun cotton fiber) in the dye bath (vat) pad dyeing piece goods by passing rapidly through the dye bathf treating raw cotton stock in a dyeing machine with the dye liquor, working yarn on beams in the dye bath, treating yarn in package dyeing machines with the dye liquor, etc.

The preparation of the dye bath or dye liquor generally involves diluting with water a vat dye paste or powder (containing the vat dye in the ordinary, unreduced form, usually after screening to insure desired fineness of the vat dye particles) and mixing it with alkali (e. g. sodium hydroxide) and a. reducing agent (e. g. sodium hydrosulfite) in suitable amounts to form a bath of the reduced (leuco) compound of the vat dye, while heating to the temperature suitable for the particular vat dye used. The resulting bath or liquor is then employed in the dyeing operation.

For ,economical dyeing it is desirable that maximum utilization of the vat dye be secured,

that the dyeings be thoroughly penetrated, and

that the color be uniform (level) and bright.

The present invention is based upon the discovery that the soluble salts of the acid reaction 0 products resulting from the interaction of a polyhydric alcohol containing less than 6 carbon atoms with one or more molecular proportions of a polybasic inorganic acidor suitable derivative thereof possess a combination of properties like, by a process in which the fiber to be dyed is treated with a non-acid dye bath or dye liquor which render them of particular value for use as containing a vat dye in the reduced (leuco) form and preferably also containing an alkali. Thus,- the soluble salts of the acid reaction products of sulfuric acid or chlorsulfonic acid upon the aliphatic polyhydric alcohols which contain 5.

or less carbon atoms, which products are considered to be acid alkyl sulfates, corresponding with the formula HOaSOROX (in which R is a I hydrocarbon radical containing not more than' 5 carbon atoms and X is H or SOaH) as well as others of the hereinafter described ester salts,

have no tendency to cause the dye liquors to foam or lather. In addition they act as assistants in the absorption or adsorption of the reduced compounds of the vat dyes by the fiber and in the penetration of woven fabric by the reduced compounds of the vat dyes. The alkyl.

ester salts of the present invention apparently act on both the vat dye and the fiber itself, causing more eifective absorption of the leucocompound of the dye.

The alkyl ester salts employed in accordance with the present invention comprise especially the soluble salts of the acid alkyl esters herein described, e. g., those resulting from the combination of any suitable metal or base, including sodium salts, in view of their extremely high a solubility in water and alkaline dye baths and 'dye liquors, are of especial value.

In dyeing with the dye baths and dye liquors which contain alkali, the free acid alkyl esters may be employed as such inasmuch as the salts of the acid alkyl esters will be formed in the bath by reaction with the alkali and there exert their advantageous action.

The said alkyl ester salts employed in accordance with the present invention ,may be prepared in any manner well known to the art; as for example, by the treatment of the corresponding polyhydric alcohol in the presence or absence of a solvent or diluent, with a suitable inorganic reagent (such as phosphorous chloride or oxychioride, concentrated sulfuric acid and/or chlorsulfonic acid, etc.), and neutralization of the resulting acid alkyl ester with an inorganic or organic base whichi'orms a readily soluble salt with said acid alkyl It may be noted that the salts of alkyl monoand di-sulfuric acids resulting from the use of sulfuric acid or chlorsul- 'tioned the various acid alkyl esters which are derivatives of polyhydric'alcohols containing not more than 5 carbon atoms; as for example, the mono-hydroxy-alkyl sulfuric, phosphoric, boric,

silicic and phosphorous acids containing not more 4 than 5 carbon atoms (derived from glycerin or various glycols containing 5 or less carbon atoms) the mono-alkyl, and mono-hydroxyalkyl, disulfuric and dlphosphoric acids containing not more than 5 carbon atoms; the diakyl, di-(hydroxy alkyl, and hydroxy alkyl-alkyl phosphoric and boric acids containing not more than 5 carbon atoms in the alkyl groups; etc. (such as, ethylene glycol monosulfuric acid, ethylene glycol disulfuric acid, ethylene glycol diphosphoric acid, glycerine disulfuric acid, glycerine mono-phosphoric acid, diglycerin boric acid, etc.)

It is to be noted, in the case of acid alkyl esters which are derivatives of polybasic acids containing 3 or more replaceable hydrogen atoms in which more than one of said hydrogen atoms have been replaced by organic radicals, the said organic radicals may be the same or different.

Mixtures of salts of the said acid alkyl esters also may be employed in accordance with the present invention. For example, the salts of suitable inorganic or organic bases with the mixtures of acid alkyl esters resulting from the sulfonation of the mixture of glycols obtained from mixed oleflnic hdyrocarbons formed in the production of gasoline by the so-called cracking process of petroleum distillation.

The percentage of assistant of the present invention that may be employed is not critical and improved results are obtained with even as little as 1 per cent or 2 per cent (based on the total weight 01' the dye bath or dye liquor) while larger proportions yield correspondingly greater improvement.

The advantageous action of the said salts of the acid alkyl esters may be secured in a number of ways. Thus the said alkyl ester salts may be incorporated into the usual dye baths and dye liquors or into the dyestuff pastes employed in preparing the dye baths and dye liquors. The said alkyl ester salts are in general crystalline prodnets and hence may be added directly to the usual dye baths or dye liquors to cause. the desired effect. Further, an advantageous action may be secured by subjecting the cloth to be dyed to a preliminary treatment with the solution of the said alkyl ester salt, as for example, impregnation. In copending application Serial No. 673,031, filed May 26, 1933, vat dye compositions in the form of powders are described containing vat dyestuffs and alkyl ester salts of the type herein disclosed. Such compositions, in view of their content of said alkyl ester salts, may be employed in accordance with the present invention merely by substituting them for the vat dye pastes usually employed, and dyeing in the ordinary manner.

If desired, foam-breaking or foam-preventing agents may also be included in the compositions of the present invention in connection with vat dyes which have a tendency to produce foaming.

The invention may be employed in connection National Carbanthrene Blue RS.

National Carbanthrene Flavine GC with vat dyes of all types including those derived from anthraquinone indophenols, various indigoid, thioindigoid and indirubin compounds, etc.; as for example, indanthrones, pyranthrones, fiavanthrones, dibenzanthrones, isodibenzanthrones, perylene quinones, anthanthrones, dibenzpyrene quinones, anthrimidocarbazols, naphthacridones, indigo, thioindigo, indirubin, .etc., including derivatives thereof, such as their halogen, nitro, sulfur, and/or alkoxy derivatives.

Examples of vat dyestuffs with which the present invention may be employed are such indigoid and thioindigoid dyestuffs as the following:

National Vat Orange R Color Index No. 1217 National Vat Red Violet RH Color Index No. 1212 5,5-dicl1lor-7,7' Dibrom Indig0. Color Index No. 1188 National Brilliant Indigo 4G Color Index No. 1189 National Brilliant Indigo B.. Color Index No. 1100 National Brilliant Indigo 4B Color Index No. 1184 National Vat Scarlet G Color Index No. 1228 Natiional Vat Brown o (dinaphthylthio 111 lgO National Vat Violet R Color IndexNo. 1222 National Vat Green G Color Index No. 1199 National Vat Pink (6, 0-dichlor-4, 4'-dimetl1yl- 2, 2-bis-thio-naphthen-indigo).

National Vat Pink BC Color Index No. 1210 National Vat Yellow G Color Index No. 1196 National Vat Yellow R Color Index No. 1170 And such anthraquinone vat dyes as the following:

Color Index No. 1106 Color Index No. 1109 Color Index No. 1113 Color Index No. 1118 Color Index No. 1097 Color Index No. 1096 Color Index No. 1173 Color Index No. 1104 Color Index No. 1099 Color Index No. 1095 Color Index No. 1161 Color Index No. 1101 Color Index No.1102 Color Index No. 1151 Color Index No. 1150 Color Index No. 1162 National Carbanthrene Blue 3G.. National Carbanthrene Blue (1C National Carbanthrene Yellow G.. National Carbanthrene Golden Orange 2RT. National Carbanthrene Golden Orange (L... National Carbanthrene Blue Green FFB. National Carbanthrene Violet 2R. National Carbanthrene Dark Blue DR.

National Carbanthrene Red Violet 2RNX- National Carbanthrene Brilliant Green supra National Carbanthrene Green B.. National Carbanthrene Brown AR. National Carbanthrene Olive R.- National Carbanthrene Red BN National Carbanthrene Red AFF Color Index No. 1133 National Carbanthrene Black I sired to produce compound shades such as scarlets, navy blues, blacks and browns. I

The invention is not restricted to any particular method of dyeing but includes the dyeing of piece goods and raw cotton stock (unspun cotton fiber) in a vat, the dyeing of piece goods (cotton, rayon, etc.) by padding in'a reduced bath, machine dyeing of raw cotton stock, dyeing of yarn (cotton or rayon) on beams or in package dyeing machines, etc.

The alkyl salts of the present invention are particularly valuable in the dyeing of so-called gray-goods (unbleached cotton fabrics, raw regenerated cellulose fabrics and the like) with vat dyes, inasmuch as the dyeings obtained with the aid of such alkyl ester salts have exceedingly high tinctorial value and excellent penetration as compared with dyeings made in the absence of said alkyl ester salts.

The following examples, in which the parts are by weight, will serve to illustrate the invention.

Example 1 Mercerized cotton piece goods are dyed in a vat (jigger) as follows:--

12.75 pounds of National Carbanthrene Blue GCD paste (containing about 17% of dye solids) are mixed with 6 pounds of disodium, or dipotassium, glycol This is particularly true for such dyes as National cellent qualty is obtained, which is then added .to the following composition contained in the jigger! Caustic soda pounds Sodium hydrosulfite (conc.) 10 pounds Water 100 gallons The temperature is raised to 110 F. and after complete reduction of the vat dye, dyeing is started at this temperature. After one passage of the goods through the bath an additional 5 pounds of sodium hydrosulfite (conc.) is added to the bath. The temperature of the bath is raised during 30 minutes to 125 F. The dyed cloth is washed once with water, is then passed four times through a sodium perborate bath (containing 2 pounds of sodium perborate per 100 gallons) at a temperature of 120- 'F., is then washed twice with cold water; passed five times through a boiling soap solution (containing 3 pounds of ordinary soap per 100 gallons), then rinsed, washed, dried and calendered.

The glycol disulfate salt may be prepared, for example, by adding 866 parts of chlorsulfonic acid to 232 parts of well-stirred ethylene glycol maintained at a temperature of about to 50 C. and maintaining said temperature until the sulfation is complete; then cooling the mixture to about 15 C. and adding it to a well-stirred solution of 400 parts of sodium carbonate (or 523 parts of potassium carbonate) dissolved inl500 parts of water to which 1500 parts of ice have been added; and recovering the disodium (or dipotas sium) glycol disulfate in the form oi a dry solid.

' Example 2 100 parts of boiled or? cotton yarn is dyed in a package dyeing machine with a dye liquor containing the following ingredients:

Parts National Carbanthrene Blue DR paste (containing about 16% of dye solids) or National Carbanthrene Violet 2R paste (containing about 11% of dye solids) 5 Caustic soda; l 2 Sodium hydrosulfite 3 Disodium, or dipotassiurn, glycol disulfate and sumcient water to give proper circu lation and dyeing conditions (e. g., about 80 to 160 parts) 3tod The conditions of dyeing are the same as usual. After dyeing, the yarn is rinsed, oxidized with 2% sodium perborate solution, rinsed, soaped,

rinsed and dried. The shades come out bright and very even.

It is obvious that, in preparing ,the dye liquors of the above examples, the ingredients may be incorporated in various ways. Further, the salt of the acid alkyl ester may'be added directly to the dye bath or may be preliminarily mixed with the vat dyestuff paste and the mixture added to the dye bath.

Instead of the glycol disulfate salts employed in the above examples, any of the other alkyl ester salts herein described may be employed.

The presence of the salts of the acid alkyl sul- I fates in the dye baths and liquors produces the following advantageous results:

(1) The dye baths are more completely exhausted;

(2) Owing to the advantageous levelling and penetrating action of the said'alkyl ester salts,

the depth of dyeing is better equalized, giving extremely even results d excellent penetration.

(3) Due to the increased penetration there is a better fixation of the dyestuif; and

(4) Due to more perfect dyeing conditions, the

brilliancy of the dyeings is enhanced.

Similar improved results may be obtained by substituting 112.75 pounds of the vat dye powder described in Example 5 oi copending application Serial No. 673,031 died May 26, 2.933 (which con tains disodium glycerin monophosphate as a part thereof) for the vat dye paste and glycol dicedfate salt of above Example 1, the amount of water being correspondingly increased.

As above indicated, the advantageous action of the salts of the acid alkyl esters as assistants in the dyeing also may be secured by pretreating the fiber with the salt of the acid alkyl ester. The following example illustrates such pretreatment.'

Example .i

Bleached or unbleached cotton cloth is padded to about 30 parts of sodium or potassium glycol disulfate, or of any of the other salts of acid aliryl esters herein described, per 1000 parts of water; for example by passing the cloth through the solution contained in a padding box equipped with squeeze rolls. Preferably, the padding liquor also contains about 2 to about 5 parts oi gum tragacanth or other suitable thickener per 1000 parts of liquor. The pressure of the squeeze rolls is preferably so regulated that the cloth retains its own weight of the padding liquor. The padded cloth is then passed through a hot air drier or over hot cans, is rolled up and is then ready for dyeing. The penetration obtained this way is superior, especially for lighter shades. This process is particularly suitable for artificial fibers of the regenerated cellulose type.

It will be understood that the dyeing process as herein described may becarried out with dye baths and dye liquors containing additional assistants such as one or more of the following: hydrotropic substances, enolyzing substances, heavy metal compoundsacting as reduction accelerators, catalysts or boosters, etc.

This application is a continuation-in-part of application Serial No. 673,031, filed May-26, 1933.

I claim:

1. In the dyeing of textile fibers by forming a non-acid solution of a leuco-conipound of a vat dye and treating the fiber with said solution, the improvement which comprisw carrying out the dyeing withthe aid of a soluble salt oi an acid alkyl ester containing not more than 5 carbon atoms in. the alkyl group and derivable from a polybasic inorganic acid and a polyhydric alcohol containing not more than 5 carbon atoms. 2. In the dyeing of textile fibers of the vegetable type by forming an alkaline solution of a 'leuco-compound of a vat dye and treating the fiber with said solution, the improvement which leucmccpound oi a vat dye and treating the 7g fiber with said solution, the improvement which comprises carrying out the dyeing in the presence of a soluble salt of an acid alkyl ester containing not more than 5 carbon atoms in the alkyl group and derivable from a polybasic inorganic acid which contains one of the radicals S02 and P and a polyhydric alcohol which contains not more than carbon atoms and not more than 3 hydroxyl groups.

4. In the dyeing of textile fibers of the vegetable type by forming an alkaline solution of a leuco-compound of a vat dye and treating the fiber with said solution, the improvement which comprises carrying out the dyeing in the presence of an alkali metal salt of an acid alkyl ester containing not more than 5 carbon atoms and derivable from a polybasic inorganic acid which contains one of the radicals S02 and PO and a polyhydric alcohol which contains not more than 5 carbon atoms and not more than 3 hydroxyl groups.

5. In the dyeing of textile fibers of the vegetable type by forming an alkaline solution of a leuco-compound of a vat dye and treating the fiber with said solution, the improvement which comprises carrying out the dyeing in the presence of an organic amine salt of an acid alkyl ester containing not more than 5 carbon atoms and derivable from a polybasic inorganic acid which contains one of the radicals SO: and PO and'a polyhydric alcohol which contains not more than 5 carbon atoms and not more than 3 hydroxyl groups.

6. In the dyeing of textile fibers of the vegetable type by treatment with a vat dye, the improvement which comprises incorporating a soluble salt of an acid alkyl ester having the formula HOsSOROX in which R represents an aliphatic hydrocarbon radical which contains not more than 5 carbon atoms and X is H or SOaH into a dye bath containing an alkaline solution of a vat dye in the reduced form, and working the fiberin the resulting dye bath.

'7. In the dyeing of textile fibers of the vegetable type by treatment with a vat dye, the improvement which comprises incorporating an alkali metal salt of a glycol disulfate containing not more than 5 carbon atoms into a dye bath containing an alkaline solution of a vat dye in the reduced form, and working the fiber in the resulting dye bath.

8. In the dyeing of textile fibers of the vegetable type by treatment with a vat dye, the improvement which comprises incorporating dipotassium glycol disulfate into a dye bath containing an alkaline solution of a vat dye in the reduced form, and working the fiber in the resulting dye bath.

9. In the dyeing of textile fibers of the vegetable type by treatment with an alkaline solution of a leuco-compound of a vat dye, the improvement which comprises treating the fiber to be dyed with a solution of a salt of an acidalkyl ester containing not more than 5 carbon atoms in the alkyl group and derivable from a polybasic inorganic acid and a pol-yhydric alcohol containing. not more than 5 carbon atoms, and subjecting the treated fiber to the dyeing process.

JEAN G. KERN. 

